Reusable nanomaterials for mitigation of persistant organic pollutants

Abstract

Provided herein are methods and systems for detecting and / or degrading harmful pollutants including PFAS. Also provided are degrading agents and detecting agents for use in provided methods.

Description

REUSABLE NANOMATERIALS EOR MITIGATION OF PERSISTANT ORGANIC POLLUTANTSPRIORITY APPLICATION

[0001] This application claims the benefit of U.S. Patent Application No. 63 / 600,494, filed November 17, 2023, the disclosure of which is hereby incorporated by reference herein in its entirety.BACKGROUND

[0002] Per- and Poly-fluoroalkyl Substances (PFAS) are widely used in various domains such as consumer, commercial, and industrial products, packaging, non-stick surfaces for household and industrial use, stain-repellant fabrics, electronics, and firefighting foams. Due to their strong carbon-fluorine (C-F) bonds that do not degrade naturally, PFAS are known as “forever chemicals” with long lifetimes. PFAS production and global consumption began around the 1950s and since then PFAS have progressively accumulated everywhere in the environment and become a serious concern to public health. In particular, owing to their long lifetimes, PFAS eventually enter the food chain to accumulate in our bodies with many adverse health effects even at very low levels. There is a need for systems and methods for detecting and degrading PFAS.SUMMARY

[0003] PFAS degradation is an energetically expensive process due to the presence of C- F bonds that are very strong and durable (e.g., C-F bond energy approximately between 450- 531.5 kJ mol1) and are resistant to typical chemical and biological degradation methods.Therefore, PFAS remediation methods typically involve only physical removal processes, such as adsorption on solid surfaces (e.g., activated carbon, ion-exchange resins, biosorbents, mineral, hybrid, or mesoporous materials) or foam fractionation. These remediation methods transfer PFAS from one phase (e.g., water) to another (e.g., foam or sorbent) requiring further treatment and disposal steps. The captured PFAS may be buried in landfills or destroyed by energy -demanding processes such as incineration, sonication, electrochemical or super-critical oxidation. PFAS degradation processes with low energy demands and performed close to standard temperature and pressure, without fractioning them into smaller PFAS fragments, are very challenging.

[0004] Presented herein are, inter alia, methods and systems for degrading and detecting, inter alia, Per- and Poly-fluoroalkyl Substances (PFAS). In certain embodiments, a sample (e.g., a gas, water, industrial waste, cleaning products) containing PFAS may be associated (e.g., adsorbed) with a degrading agent (e.g., to remove PFAS from the sample by effectively reducing its concentration in the sample) to form a degradation complex or with a detecting agent to form a detection complex (e.g., detecting one or more species of PFAS in the sample, e.g., by emitting a signal in response to the presence of PFAS in a sample). In some embodiments, a degradation complex may be further exposed to one or more degradation activators, which are substances that, when associated with a degradation complex result in the degradation of at least a portion of PFAS. In some embodiments, a detection complex may be exposed to one or more detection activators. In certain embodiments, degradation activators or detection activators are or comprise hydrogen gas that is catalyzed by the degradation complex or detection complex to react with PFAS (e.g., under room temperature and atmospheric pressure). As a result, the exposure process degrades PFAS (e.g., by breaking carbon-fluorine bonds) or causes a signal to be propagated in detection applications. In certain embodiments, the degrading agent and / or detecting agent may be regenerated after the exposure and / or reused.

[0005] Also presented herein are methods and systems for making degrading agents and detecting agents for degrading and detecting PFAS, respectively. In certain embodiments, a degrading agent and / or a detecting agent may be comprised of a substrate, a buffer layer, a plurality of nanoscale attachments, and, in some embodiments, one or more capture agents. In some embodiments, a buffer layer may be composed of silica coating to create binding sites to attach, for example, a plurality of nanoscale attachments. In some embodiments, a plurality of nanoscale attachments may be or comprise a plurality of carbon nanotubes (CNT) to provide high surface area for increased reactivity (this may be referred to herein as a “nanotube carpet”). In some embodiments, a plurality of nanoscale attachments may be or comprise one or more capture agents, for example nanoparticles, attached to carbon nanotubes (CNT) to provide highsurface area for increased reactivity (this may be referred to herein as a “nanoparticle carpet”) In some embodiments, a nanoparticle carpet may comprise a plurality of nanoparticles (e.g., palladium nanoparticles) to degrade PFAS in the presence of degradation activators (e.g., hydrogen gas). In certain embodiments, a degrading and / or a detecting agent may comprise one or more capture agents (e.g., ionomers or nanoparticles) to selectively capture (e g., bind or otherwise associate with) and / or detect PFAS species. In certain embodiments, a degrading and / or detecting agent may be further modified to have altered wettability to improve interaction with a sample as compared to a non-modified degrading and / or detecting agent, respectively.

[0006] The present disclosure provides, in accordance with various embodiments, methods for degrading Per- and Poly-fluoroalky 1 Substances (PFAS) including providing a sample comprising one or more PFAS, associating the sample with a degrading agent to form a degradation complex, and exposing at least a portion of the degradation complex to one or more degradation activators.

[0007] The present disclosure also provides methods for detecting Per- and Polyfluoroalkyl Substances (PFAS) comprising providing a sample, associating the sample with a detecting agent to form a detection complex if the sample comprises one or more PFAS, receiving a signal from the detection complex, wherein the signal indicates a presence of one or more PFAS in the sample. In some embodiments, a signal comprises at least one member selected from the group consisting of an electrical, electrochemical, optical, thermal, spectral, and / or chemical signal. In some embodiments, the strength of a signal is related to a PFAS concentration of one or more PFAS. In some embodiments, provide methods comprise modifying one or more PFAS (e.g., into a different compound by braking carbon-fluorine bonds) after the exposing of at least a portion of the detection complex to the one or more detection activators.

[0008] In some embodiments, a sample is or comprises a gas or a liquid. In some embodiments, a sample is or comprises air, water, industrial waste, foodstuffs, cleaning products, shampoo.

[0009] In some embodiments, provided methods may further include a step of pretreating the sample (e.g., mechanical fdtration, pH adjustment, removal of chlorine, iron, surfactants, total organic carbon).

[0010] In accordance with various embodiments, any application-appropriate manner of associating may be used. In some embodiments, associating comprises at least one member selected from the group consisting of causing surface contact, adsorption, mechanical adhesion, chemical adhesion, dispersive adhesion, diffusive adhesion, infdtration through pores.

[0011] It is contemplated that exposing a degradation complex or detection complex to a degradation activators or detection activator, respectively, can occur under any of a variety of conditions. For example, in some embodiments, exposing occurs at room temperature and / or normal pressure (i.e. approximately 1 atmosphere). In some embodiments, exposing occurs in a gas stream or in a liquid. In some embodiments, degradation activators comprise hydrogen or a mixture of hydrogen and inert gases (e.g., nitrogen). In some embodiments, degradation activators or detection activators may be or comprise at least one member selected from the group consisting of hydrogen gas, nitrogen gas, visible illumination, ultraviolet illumination, near-infrared illumination, infrared illumination, microwave illumination, plasma activation, electrical activation.

[0012] In some embodiments, a degrading agent and / or detecting agent may be regenerated. In some embodiments, regenerating (e.g., renewing) at least a portion of a degrading agent or detection agent may occur after associating the sample with the degrading agent or detecting agent and / or exposing to the one or more degradation activators or detection activators. In some embodiments, regenerating is or comprises exposing at least a portion of the degrading agent to a solvent (e.g., methanol and / or ethanol), exposing at least a portion of the degrading agent to an acid, or exposing at least a portion of the degrading agent to an elevated temperature.

[0013] It is contemplated that under actual use conditions, a sample may not be substantially pure. Accordingly, in some embodiments, PFAS are present in the sample with one or more co-contaminants. In some embodiments, a co-contaminant may be or comprise a metal, a salt, or organic matter.

[0014] In some embodiments, provided methods may further include modifying one or more PFAS (e.g., into a different compound by breaking carbon-fluorine bonds) after the exposing of at least a portion of the degradation complex to the one or more degradation activators.

[0015] In some embodiments, at least a portion of a provided method is performed in and / or connected to a water treatment system (e.g., purification system, filtration system, distillation system, reverse osmosis system, ion exchange system, disinfection system, electrochemical system).

[0016] In accordance with various embodiments, the present disclosure provides systems for degrading and / or detecting Per- and Poly-fluoroalkyl Substances (PFAS) by performing a method described herein.

[0017] The present disclosure also provides methods of making a degrading agent or a detecting agent including providing a substrate, applying a deposition reaction to at least a portion of the substrate to form a buffer layer, applying a chemical vapor deposition reaction to at least a portion of the buffer layer to form a plurality of nanoscale attachments on the substrate.

[0018] In some embodiments, such methods further include associating a plurality of nanoparticles or a nanolayer with at least a portion of the plurality of nanoscale attachments. In some embodiments, nanoparticles are or comprise a metal or a metal oxide. In some embodiments, the metal is or comprises palladium. In some embodiments, the oxide is or comprises a photocatalyst. In some embodiments, nanoparticles are or comprise a sulfide, a carbide, or a polymeric moiety. In some embodiments, one or more catalytic agents are attached to at least a portion of the plurality of nanoscale attachments and / or the nanoparticles. In some embodiments, at least a portion of the nanoparticles are or comprise metallic Pd nanoparticles with an average diameter between about 2 nm to about 50 nm (e.g., between about 2 nm to about 15 nm). In some embodiments, at least a portion of the nanoparticles are or comprises at least one type of nanoparticle with catalytic properties [e.g., metallic catalysts such as palladium, semiconductor nanoparticles (e.g., ZnS, CdTe, HgSe, heterojunction semiconductors); oxides (e.g., TiCh, ZnO, WO3); plasmonic materials (e.g., gold, silver), alloys; composites; metalorganic frameworks; covalent organic frameworks; hydrogen-bonded organic frameworks]. In some embodiments, at least a portion of the nanoparticles are or comprise WO3 nanoparticles. In some embodiments, at least a portion of the nanoparticles are or comprise TiCh nanoparticles.

[0019] Any of a variety of substrates are contemplated for use in various embodiments. In some embodiments, a substrate may be selected at least in part for its ability to withstand one or more adverse conditions (e.g., high heat, high pressure). In some embodiments, a substratemaintains its structural integrity to at least 700 °C. In some embodiments, a substrate is or comprises at least one of a carbon structure (e.g., foam, cloth, pellets, paper, fabric), ceramic material, glass, an oxide or metal foam.

[0020] A variety of methods for depositing a plurality of nanoscale attachments on a substrate are contemplated. By way of non-limiting example, in some embodiments, depositing may occur via any known deposition reaction. In some embodiments, a deposition reaction may be or comprise a plasma enhanced chemical vapor deposition reaction. In some embodiments, a chemical vapor deposition reaction comprises exposing at least a portion of the substrate to a mixture of precursor materials (e.g., hexa-methyldisiloxane or HMDSO) and gases (e.g., oxygen).

[0021] In some embodiments, a buffer layer may be formed during production of a degrading agent or a detection agent. In some embodiments, a buffer layer thickness is between about 1 nm to about 50 nm.

[0022] In some embodiments, a plurality of nanoscale attachments is or comprises a layer of one-dimensional nano-structures. In some embodiments, one-dimensional structures are or comprises nanotubes (e.g., carbon, nitride, carbide, oxide, metal). In some embodiments, at least a portion of the layer of one-dimensional structures is covalently bonded to the substrate. In some embodiments, a layer of nanotubes is between about 1 pm to about 2000 pm in height. In some embodiments, a layer of nanotubes has an average density between about 10 to about 1,000 units per pm2. In some embodiments, a layer of nanotubes has an average diameter between about 2 to about 30 nm. In some embodiments, a layer of nanotube has an estimated specific surface area between about 70 to about 150 m2 / g.

[0023] In some embodiments, a coating may be applied to at least a portion of the nanoscale attachments (e.g., nanotubes). In some embodiments, coating may be or include at least one of plasma oxygen coating on the nanoscale attachments (e g., nanotubes) for a short duration (e.g., 5 s), and coating the layer of nanoscale attachments (e.g., nanotubes) with a solgel silica coating followed by controlled heating.

[0024] The present invention also provides degrading agents and detecting agents including a substrate, and a plurality of nanoscale attachments associated with the substrate,wherein the plurality of nanoscale attachments. Tn some embodiments, at least a portion of the nanoscale attachments are formed by liquid or vapor phase treatments.

[0025] In accordance with various embodiments, degrading agents or detecting agents may further include a plurality of capture agents associated with at least a portion of the plurality of nanoscale attachments. In some embodiments, a plurality of capture agents are or comprise nanoparticles.BRIEF DESCRIPTION OF THE DRAWING

[0026] The present teachings described herein will be more fully understood from the following description of various illustrative embodiments, when read together with the accompanying figures. It should be understood that the figures described below are for illustration purposes only and are not intended to limit the scope of the present teachings in any way. The foregoing and other objects, aspects, features, and advantages of the disclosure will become more apparent and may be better understood by referring to the following description taken in conjunction with the accompanying figures, in which:

[0027] FIG. 1 shows an example schematic of a liquid purification system with an embedded degrading agent.

[0028] FIG. 2 shows a schematic of an example system that can be used to form a plurality of nanoscale attachments.

[0029] FIG. 3 shows a set of photographs of an example degrading agent at various scales.

[0030] FIG. 4 shows a schematic of an example pathway for stepwise Perfluorooctanoic Acid (PFOA, one of the most commonly occurring PFAS species) degradation in the presence of palladium and hydrogen.

[0031] FIG. 5 shows an example set of results for PFAS associating with a degrading agent.

[0032] FIG. 6 shows a schematic of an example of degrading agent.

[0033] FIG. 7 shows a schematic of an example system that can be used to form a buffer layer.

[0034] FIG. 8 shows a schematic of an example system that can be used for PFAS degradation and / or detection.

[0035] FIG. 9 shows an exemplary electrochemical system employed for PFAS detection.

[0036] FIG. 10 shows an example of electrochemical measurements by detecting agents in the presence of Perfluorooctanoic Acid (PFOA, one of the most commonly occurring PFAS species).

[0037] FIG. 11A shows an example of PFOA adsorption after association with a degrading agent.

[0038] FIG. 11B shows an example of PFOA association with a degrading agent.

[0039] FIG. 11C shows an example of PFOA association with a degrading agent.

[0040] FIG. 11D shows an example of PFOA desorption from a degrading agent.DEFINITIONS

[0041] About: The term “about”, when used herein in reference to a value, refers to a value that is similar, in context to the referenced value. In general, those skilled in the art, familiar with the context, will appreciate the relevant degree of variance encompassed by “about” in that context. For example, in some embodiments, the term “about” may encompass a range of values that are within 25%, 20%, 19%, 18%, 17%, 16%, 1 %, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, or less of the referred value.

[0042] Agent: As used herein, the term “agent”, may refer to a physical entity or phenomenon. In some embodiments, an agent may be characterized by a particular feature and / or effect. In some embodiments, an agent may be a compound, molecule, or entity of any chemical class including, for example, a small molecule, polypeptide, nucleic acid, saccharide, lipid, metal, or a combination or complex thereof. In some embodiments, the term “agent” may refer to a compound, molecule, or entity that comprises a polymer. In some embodiments, theterm may refer to a compound or entity that comprises one or more polymeric moieties. In some embodiments, the term “agent” may refer to a compound, molecule, or entity that is substantially free of a particular polymer or polymeric moiety. In some embodiments, the term may refer to a compound, molecule, or entity that lacks or is substantially free of any polymer or polymeric moiety. In some embodiments, an agent may be or comprise a system or device. In some embodiments, an agent may be or comprise a force such as an electric force, a gravitational force, a magnetic force, etc.

[0043] Associated: Two events or entities are “associated” with one another, as that term is used herein, if the presence, level, degree, type and / or form of one is correlated with that of the other. In some embodiments, two or more entities are physically “associated” with one another if they interact, directly or indirectly, so that they are and / or remain in physical proximity with one another. In some embodiments, two or more entities that are physically associated with one another are covalently linked to one another; in some embodiments, two or more entities that are physically associated with one another are not covalently linked to one another but are non- covalently associated, for example by means of hydrogen bonds, van der Waals interaction, hydrophobic interactions, magnetism, and combinations thereof.

[0044] Comprising: A composition or method described herein as "comprising" one or more named elements or steps is open-ended, meaning that the named elements or steps are essential, but other elements or steps may be added within the scope of the composition or method. To avoid prolixity, it is also understood that any composition or method described as "comprising" (or which "comprises") one or more named elements or steps also describes the corresponding, more limited composition or method "consisting essentially of (or which "consists essentially of) the same named elements or steps, meaning that the composition or method includes the named essential elements or steps and may also include additional elements or steps that do not materially affect the basic and novel character! stic(s) of the composition or method. It is also understood that any composition or method described herein as "comprising" or "consisting essentially of one or more named elements or steps also describes the corresponding, more limited, and closed-ended composition or method "consisting of (or "consists of) the named elements or steps to the exclusion of any other unnamed element orstep. In any composition or method disclosed herein, known or disclosed equivalents of any named essential element or step may be substituted for that element or step.

[0045] Moiety Those skilled in the art will appreciate that a “moiety” is a defined chemical group or entity with a particular structure and / or activity, as described herein.

[0046] Nanoscale attachment: As used herein, the term "nanoscale attachment" refers to a discrete entity thar has the smallest dimension between l-100nm and is capable of associating (e.g., binding) with or to at least one PFAS and / or capture agent.

[0047] Nanoparticle: As used herein, the term “nanoparticle” refers to a discrete entity of small size, e.g., typically having a longest dimension that is shorter than about 1000 nanometers (nm) and often is shorter than 500 nm, or even 100 nm or less. In many embodiments, a nanoparticle may be characterized by a longest dimension between about 1 nm and about 100 nm, or between about 1 pm and about 500 nm, or between about 1 nm and 1000 nm. In many embodiments, a population of microparticles is characterized by an average size (e.g., longest dimension) that is below about 1000 nm, about 500 nm, about 100 nm, about 50 nm, about 40 nm, about 30 nm, about 20 nm, or about 10 nm and often above about 1 nm. In many embodiments, a microparticle may be substantially spherical (e.g., so that its longest dimension may be its diameter). In some embodiments, a nanoparticle has a diameter of less than 100 nm as defined by the National Institutes of Health. In some embodiments, nanoparticles are micelles in that they comprise an enclosed compartment, separated from the bulk solution by a micellar membrane, typically comprised of amphiphilic entities which surround and enclose a space or compartment (e.g., to define a lumen). In some embodiments, a micellar membrane is comprised of at least one polymer, such as for example a biocompatible and / or biodegradable polymer.

[0048] Specific binding: As used herein, the term “specific binding” refers to an ability to discriminate between possible binding partners in the environment in which binding is to occur. A binding agent that interacts with one particular target when other potential targets are present is said to "bind specifically" to the target with which it interacts. In some embodiments, specific binding is assessed by detecting or determining degree and / or rate of association between the binding agent and its partner; in some embodiments, specific binding is assessed by detecting or determining degree and / or rate of dissociation of a binding agent-partner complex;in some embodiments, specific binding is assessed by detecting or determining ability of the binding agent to compete an alternative interaction between its partner and another entity. In some embodiments, specific binding is assessed by performing such detections or determinations across a range of concentrations.

[0049] Substantially: As used herein, the term “substantially” refers to the qualitative condition of exhibiting total or near-total extent or degree of a characteristic or property of interest. One of ordinary skill in the biological arts will understand that biological and chemical phenomena rarely, if ever, go to completion and / or proceed to completeness or achieve or avoid an absolute result. The term “substantially” is therefore used herein to capture the potential lack of completeness inherent in many biological and chemical phenomena.DETAILED DESCRIPTION

[0050] It is contemplated that compositions, methods, and processes of the present application encompass variations and adaptations developed using information from embodiments described in the following description. Adaptation and / or modification of compositions, methods, and processes described in the following description may be performed by those of ordinary skill in the relevant art.

[0051] Throughout the description, where compositions are described as having, including, or comprising specific components, or where processes and methods are described as having, including, or comprising specific steps, it is contemplated that, additionally, there are aspects of the present application that consist essentially of, or consist of, recited components, and that there are processes and methods according to the present application that consist essentially of, or consist of, recited processing steps.Methods for Degrading and / or Detecting PF AS

[0052] In certain embodiments, methods for degrading and / or detecting PFAS may comprise any of the following steps. Providing a sample (e.g., a gas, a liquid such as water, industrial waste, cleaning products) containing one or more species of PFAS that is associated (e.g., adsorbed) with a degrading agent to form a degradation complex (e g., to remove PFAS from the sample by, e.g., effectively reducing its concentration in the sample) or a detectingagent to form a detection complex (e.g., detecting one or more species of PFAS in the sample, e.g., by emitting a signal in response to the presence of PFAS in a sample). In some embodiments, a degradation complex is exposed to one or more degradation activators. In some embodiments, a detection complex is exposed to one or more detection activators. In certain embodiments, degradation activators or detection activators comprise hydrogen gas, nitrogen or inert gas, visible illumination, ultraviolet illumination, near-infrared illumination, infrared illumination, microwave illumination, plasma activation, electrical activation, or any combination thereof. In some embodiments, a degradation activator [e.g., hydrogen gas, light (e.g., visible, ultraviolet, near-infrared, infrared, etc.)] may be catalyzed by a degradation complex to react with PFAS under room temperature and atmospheric pressure. As a result, the exposure process degrades PFAS (e.g., by breaking carbon-fluorine bonds).

[0053] In some embodiments, provided methods and systems modify one or more PFAS. In some embodiments modification may be or comprise breaking carbon-halogen bonds and / or mineralization.

[0054] In certain embodiments, methods of detecting PFAS may comprise receiving a signal from a detection complex. In certain embodiments, a signal may indicate a presence of PFAS in a sample. In certain embodiments, the strength of a signal may be related to a PFAS concentration in a sample (e.g., more PFAS in a sample results in a stronger signal). In certain embodiments, a signal may comprise electrical, electrochemical, optical, thermal, chemical, enzymatic, or any combination thereof.

[0055] In certain embodiments, methods for degrading and / or detecting PFAS may be performed at least in part in and / or connected to liquid treatment systems, such as purification system, filtration system, sedimentation system, distillation system, reverse osmosis system, ion exchange system, disinfection system, electrochemical system, or any combination thereof.

[0056] FIG. 1 demonstrates an example of a liquid purification system with an embedded degrading agent. The system 100 may comprise at least one inlet 101, at least one inlet valve 102, a degrading activator 103, an activator valve 104, a reaction chamber 105 with the embedded degrading agent 106 (e.g., a micrograph of a degrading agent example is 107), at least one outlet valve 108, and two outlets 109 and 110.

[0057] In certain embodiments, a degrading agent may be validated by comparing its performance in terms of association and degrading activity against other adsorptive media (e.g., granular activated carbon (GAC), an ion exchange resin (IX)) using isotherm testing and column testing. Further, in some embodiments, test waters from full-scale systems operated by industrial and governmental operators may be used to validate the adsorption of the degrading agent against other media types.

[0058] In certain embodiments, performance of a degrading agent as characterized by association and / or degrading activity may be validated using small column tests at a water treatments site. In some embodiments, at least one of dynamic capacity and time to breakthrough may be assessed. These column tests may mimic critical design parameters of full-scale systems.

[0059] In certain embodiments, performance of a degrading agent as characterized by association and / or degrading activity may be validated by measuring fluoride released into the system solution relative to the amount of organofluorine that is loaded into the media prior to the measurement. In some embodiments, durability of a degrading agent over multiple cycles may be inspected visually for any obvious physical breakdown of the agent.

[0060] Prior to the present disclosure, PFAS detection was limited by the need for complex analytical techniques and slow turn-around times. Conventional detection methods for PFAS in environmental matrices require high resolution mass spectrometry (HRMS) techniques such as liquid chromatography tandem mass spectrometry (LC-MS / MS) at centralized facilities with highly trained technicians.

[0061] Described herein are also methods and systems for portable PFAS detection. In certain embodiments, a detecting element is or comprises a sensing electrode for electrochemical PFAS detection. A sensing electrode designed to detect a sample may comprise at least two components: a “receptor” or a probe, and a “transducer”. A receptor is an interactive “sensitive” component that undergoes detectable change(s) in proximity with a sample. A transducer is a component that is in close contact with the receptor and transmits the change in the receptor into a measurable (e.g., electrical) signal. In certain embodiments, the analyte-receptor-transducer interface determines both the sensitivity and selectivity of the signal.

[0062] In principle any electrochemical method may be used for the detection of PFAS in a sample. By way of example only, in some embodiments, electrochemical detection methodsinclude potentiometry (e.g., methods to measure potential of a solution between two electrodes), coulometry (e.g., methods to quantify number of electrons needed to convert a sample from one oxidation state to another), and voltammetry (e.g., methods to apply a varying or constant potential and to measure the resulting current, amperometry). A voltammetry setup may comprise at least two electrodes (usually three) and a conducting medium between them. A working electrode contacts a sample, applies desired potential in a controlled manner. A second electrode, often called a reference electrode, maintains a known potential. A third electrode, known as a counter electrode, also called an auxiliary electrode, allowing the current to flow between the counter electrode and working electrode, to protect the potential of reference electrode against shifting. Voltammetry may include linear sweep voltammetry (e.g., electrode potential is swept linearly with time and current is recorded), staircase voltammetry (e.g., voltage is applied for a certain period that is followed by a current measurement in a staircase manner), squarewave voltammetry (e.g., voltage is applied combining a square wave and staircase potential and current is recorded), cyclic voltammetry (e.g., voltage is scanned in a circular manner linearly with time, current is recorded), anodic stripping voltammetry (e.g., a sample is deposited onto the working electrode and then oxidized, current is recorded during oxidation), cathodic stripping voltammetry (e.g., positive potential oxidizes mercury electrode to form insoluble precipitates and then negative potential strips the precipitates into solution), adsorptive stripping voltammetry (e.g., a sample is deposited by adsorption on the electrode and then electrolyzed to produce the signal), alternative current voltammetry (e.g., small sinusoidal oscillations of potential are combined with varying overall voltage), polarography (e.g., a working electrode is a dropping mercury electrode), rotated electrode voltammetry (e.g., a working electrode is a rotating disk electrode or a rotating ring-disk electrode), normal pulse polarography (e.g., potential is applied in pulses each starting at the same level but amplitude increases with every step), normal pulse voltammetry (e.g., similar as the normal pulse polarography, but may be used with non-polarographic electrodes), differential pulse voltammetry (e.g., similar to normal pulse voltammetry, but the pulse base is increased or decreased steadily and the pulse height is kept constant), chronoamperometry (e.g., potential is varied and current is recorded), or any combination thereof.Per- and Poly-fluoroalkyl Substances (PF AS)

[0063] Per- and Poly-fluoroalkyl Substances, also referred to herein as PFAS, correspond to a group of synthetic organofluorine chemical compounds that have multiple fluorine atoms attached to an alkyl chain. In some embodiments, PFAS contain at least one perfluoroalkyl moiety, -CnF2n i-. In some embodiments, PFAS are fluorinated substances that contain at least one fully fluorinated methyl or methylene carbon atom (e.g., without any H / Cl / Br / I atom attached to it). For example, with a few exceptions, any chemical with at least a perfluorinated methyl group (-CF3) or a perfluorinated methylene group (-CF2-) may be a PFAS. The most prevalent PFAS in the environment can be classified as Perfluoroalkyl acids (PFAAs), Perfluoroalkyl carboxylates (PFCAs), Perfluoroalkane sulfonates (PFSAs), and Perfluoroalkane sulfonamides (FASAs). According to various resources, there are from 4700 to 6 million unique PFAS compounds.

[0064] Currently, PFAS are used in a wide variety of products, including carpet, leather and apparel, textiles, paper and packaging, coatings, rubber, plastics. Previously, PFAS were used in the food industry products (e g., cookware) due to their enhanced water-resistant properties (e.g., Teflon). In cosmetics, PFAS are used for lipstick, eye liner, mascara, foundation, concealer, lip balm, blush, and nail polish. In terms of occupational exposure, there are more than 200 different ways PFAS are used in various industries (e.g., electronics and equipment manufacturing, plastic and rubber production, food and textile production, building and construction). In ski industry, glide wax, used to coat the bottom of skis to reduce the friction between the skis and snow, may contain PFAS. In firefighting and military, PFAS may be used in Class B firefighting foams and flame-resistant protective gear (e.g., owing to PFAS hydrophobic and lipophobic properties, as well as the stability when exposed to high heat).

[0065] PFAS may be described as “forever chemicals” due to their strong chemical bonds, leading them to remain in the environment for long periods of time. The prolonged lifetime and constant industrial use result in PFAS accumulation in drinking water, rainwater, municipal wastewater and landfill leachates worldwide. This accumulation leads to extended PFAS exposure to humans confirmed in multiple instances.

[0066] PFAS are associated with numerous human health concerns as, for example, dyslipidemia, suboptimal antibody response, reduced infant and fetal growth, higher rates ofkidney cancer. Among others, the presence of PF AS has an impact on immune function with reports indicating reduction in diphtheria antibody concentration in children after exposure to perfluorooctane sulfonate through maternal serum. Other reports indicate a link between PFAS exposure and thyroid disease with sex-specific outcomes. Other experimental evidence point to PFAS toxicity in liver as a primary target of PFAS storage. Other evidence reveals that PFAS increases serum total and low-density lipoprotein cholesterol in children and adults. Due to further reabsorption of PFAS by kidneys, reports also indicate PFAS role in kidney disease and kidney cancer. Finally, exposure to PFAS impairs human sperm motility and sperm penetration, affecting long-term reproductive and developmental functions.

[0067] Several technologies are currently used for PFAS removal from liquids. For example, PFAS remediation methods may involve physical removal processes such as adsorption on solid surfaces (e.g., activated carbon, ion-exchange resins, biosorbents, mineral, hybrid, or mesoporous materials) or foam fractionation. These remediation methods transfer PFAS from one phase (e.g., water) to another (e.g., foam or sorbent) requiring further treatment and disposal steps. The captured PFAS may be buried in landfills or destroyed by energy-demanding processes such as incineration, sonication, electrochemical or super-critical oxidation. The efficiency and operating costs of various technologies may vary with water quality parameters (e.g., pH, contaminants).

[0068] Some embodiments of provided technologies may benefit in terms of efficiency and operating costs from a pretreating a sample (e.g., mechanical filtration, pH adjustment, removal of chlorine, iron, surfactants, total organic carbon).

[0069] In certain embodiments, PFAS are present in the sample with one or more cocontaminants (e.g., metals, salt, organic matter, FeSC>4- H2O, ZnCh, NiSO4-6H2O, CuSO4-5H2O, MgCh-6H2O, KC1, KNO3, NaCl) that may need to be removed, interfere with the technology, reduce efficiency of the technology, or any combination thereof. In accordance with various embodiments, common co-contaminants and detecting / characterizing them may include one or more of total dissolved solids and conductivity as represented by additions of sodium chloride, sodium sulfate, magnesium chloride, and calcium nitrate, total hardness, iron concentrations (ferrous and ferric), and other metals such as nickel, copper and zinc, organics, represented by aproxy of total organic carbon, and surfactants, such as cetyltrimethylammonium (CTAB) and cocamidopropyl hydroxy sultaine (CAHS).Samples

[0070] In accordance with various embodiments, any of a variety of samples including one or more PF AS may be appropriate for various embodiments. For example, in some embodiments, a sample may be or comprise a gas, a liquid, water, industrial waste, cleaning products, water-resistant fabrics, grease-resistant paper, shampoo, eye makeup, stain-resistant coatings, and any other PFAS containing compound or composition. In some embodiments, a gas may be a pure gas with a substantially uniform composition. In some embodiments, a gas may comprise two or more distinct species of gas. In some embodiments, a liquid may be or comprise a single liquid (e.g., water). In some embodiments, a liquid may comprise two or more distinct liquids.Degrading and Detecting Agents

[0071] In accordance with various embodiments, a degrading agent or a detecting agent comprises at least one substrate and a plurality of nanoscale attachments that are associated with the at least one substrate. In some embodiments, one or more capture agents are associated with at least some of the plurality of nanoscale attachments. In accordance with the disclosure, a degrading agent and a detecting agent may be substantially the same apart from different capture agents.Substrates

[0072] In accordance with various embodiments, any application-appropriate substrate may be used. In certain embodiments, a substrate may comprise at least one of carbon structures (e.g., foam, cloth, pellets, paper), ceramics, clay, glass, oxides, metal foam.

[0073] In certain embodiments, a substrate may comprise a high surface area material with thermal stability in a controlled environment (e.g. reducing environment of the deposition process) to at least 700 °C (e.g., carbon foams, metallic foams, oxide foams, boron nitride foams,carbon fabric). In some embodiments, a substrate may set a robust scaffold for subsequent nanomaterials attachments. In certain embodiments, a substrate maintains its structural integrity to at least 700 °C (e.g., to sustain subsequent fabrication steps). In certain embodiments, a substrate is chemically inert to subsequent fabrication steps.Nanoscale Attachments

[0074] In certain embodiments, a plurality of nanoscale attachments may be composed of a layer of one-dimensional structures, for example, a layer of nanotubes (e.g. carbon, nitride, carbide, oxide, metal). Some species of nanotubes are acid and alkali resistant, hydrophobic, and good adsorbents for PFAS. The nanoscale attachments may provide high surface area for increased reactivity with PFAS. In certain embodiments, nanoscale attachments may contain defects (e.g., atomic, molecular, crystallographic, point, line, surface, volume) for at least one of selective chemical attachment of the intended target (e.g., PFAS) and optical identification (e g., luminescence, scattering). The layer of nanoscale attachments may be between about 1 pm and about 2000 pm. The layer of nanotubes may have an average density between about 10 and about 10,00 units per pm2. The layer of nanotubes may have an average diameter between about 5 and about 30 nm. The layer of nanoscale attachments may have an estimated specific surface area between about 70 and about 150 m2 / g. In some embodiments, nanotube distribution / density may be between 8* 109to 5* 10nCNTs / cm2.

[0075] In certain embodiments, a chemical vapor deposition reaction may be used to form nanoscale attachments. In certain embodiments, a chemical vapor deposition comprises: (a) exposing the buffer layer to a mixture of gases injected at 235 °C, wherein the mixture of gases comprises one or more of xylene, ferrocene, argon, and hydrogen; (b) heating the buffer layer to 800 °C in the presence of the mixture of gases; (c) keeping the buffer layer at 800 °C in the presence of the mixture of gases for a period of time; (d) allowing the buffer layer to cool overnight in an inert gas (e.g., argon). The period of time may be between about 5 minutes and 2 hours.

[0076] FIG. 2 shows a schematic that represents an example system 200 to form a plurality of nanoscale attachments. The system 200 may comprise an argon inlet 201, hydrogen inlet 202 that both lead to a reaction chamber 203 with a substrate 204 and an inlet 205.Capture Agents

[0077] In accordance with various embodiments, a capture agent may have any of a variety of forms so long as the capture agent(s) is able to bind the intended target (e.g., PFAS) and associate with at least a portion of the plurality of nanoscale attachments. In some embodiments, a capture agent is or comprises one or more ionomers, nanoparticles, molecularly imprinted polymers (MIP), or moieties that bind to specific molecules. In some embodiments, nanoscale attachments by themselves or their defects (e.g., atomic, molecular, crystallographic, point, line, surface, volume) may act as capture agents. In some embodiments a capture agent is useful in detecting the intended target (e g., PFAS). In some embodiments a capture agent is useful in degrading the intended target (e.g., PFAS).

[0078] In some embodiments, a capture agent may be or comprise one or more nanoparticles. In certain embodiments, a plurality of nanoparticles may be associated (e.g., attached, grown onto) with the plurality of nanoscale attachments. In some embodiments, nanoparticles may perform catalytic function to degrade PFAS. In some embodiments, nanoparticles may be important in the detection of PFAS. In certain embodiments, nanoparticles comprise a metal, an oxide, a sulfide, a carbide, a polymeric moiety, or any combination thereof. In certain embodiments, a metal comprises palladium. In certain embodiments, an oxide comprises a photocatalyst.

[0079] In certain embodiments, a plurality of nanoparticles comprises at least one type of nanoparticles with catalytic properties [e.g., palladium nanoparticles, semiconductor nanoparticles (e.g., ZnS, CdTe, HgSe, heterojunction semiconductors); oxides (e.g., TiCh, ZnO, WO3); plasmonic materials (e.g., gold, silver), alloys; composites; metal-organic frameworks; covalent organic frameworks; hydrogen-bonded organic frameworks]. Nanoparticles may have an average diameter between about 2 nm and about 50 nm. In certain embodiments, nanoparticles are or comprise WO3 nanoparticles. In certain embodiments, nanoparticles have specific defects that determine their properties. In certain embodiments, nanoparticles are or comprise palladium nanoparticles.

[0080] In certain embodiments, nanoparticles are or comprise TiCh nanoparticles. Without wishing to be held to a particular theory, supporting TiCh on CNT may enhance catalytic activity, possibly by increasing surface area, may enhance pollutant adsorption, may induce visible light response, and / or may boost electron-hole separation.

[0081] In certain embodiments, palladium nanoparticles are formed by a liquid-phase synthetic approach. In some embodiments, the approach comprises: (a) soaking the nanoscale attachments in a tetra-amine palladium nitrate solution; (b) recovering the nanoscale attachments from the tetra-amine palladium nitrate solution; (c) washing-off the excess of the solution from the nanoscale attachments by briefly rinsing the substrate with deionized (DI) water and methanol; (d) drying the nanoscale attachments at 100 °C; (e) calcinating the nanoscale attachments at 400 °C in inert atmosphere (e.g. argon), (f) annealing the nanoscale attachments at 450 °C in reducing environment containing hydrogen-argon mixture as the carrier gas. The tetraamine palladium nitrate solution may have a concentration between about 1 mM and about 1000 mM. Pd nanoparticles may be formed with an average fractional Pd concentration between about 1 % to about 25 % by weight.

[0082] FIG. 3 shows a set of photographs of an exemplary degrading agent at various scales. Photographs 301, 302, and 303 demonstrate micrographs of a plurality of nanoscale attachments with associated nanoparticles. A photograph 304 demonstrates a degrading agent example.

[0083] When used in agents and methods described herein, in accordance with various embodiments, palladium (Pd) nanoparticles in the presence of hydrogen enable defluorination of Perfluorooctanoic Acid (PFOA). The activity of these materials may be improved by carbon supports. Pd nanoparticles attached to CNT carpets show significantly higher rate and capacity for catalytic degradation of C-Cl bonds compared to unattached CNT- Pd nanocatalysts. With regards to C-F bond, the bond energy is about 33% higher (439 kJ / mol for C-F vs 330 kJ / mol for C-Cl), but if the Pd particle size is sufficiently small, stepwise destruction of PFAS will follow eventually leading to defluorinated molecules.

[0084] FIG. 4 shows a schematic of an example pathway for stepwise PFOA degradation in the presence of palladium.

[0085] In some embodiments, a degrading agent or a detecting agent may comprise an improvement. In some embodiments, an improvement comprises a plurality of chemically strong (e.g., covalent) bonds. In some embodiments, chemically strong bonds may be between a substrate and a plurality of nanoscale attachments. In some embodiments, chemically strong bonds may be between a buffer layer and a plurality of nanoscale attachments. In someembodiments, chemically strong bonds may be between a plurality of nanoscale attachments and nanoparticles. In accordance with various embodiments, strong bonds may enhance agent stability and / or prevent agent deterioration during use. In some embodiments, durability tests performed on a degrading agent or a detection agent may show that the agent sustains prolonged use in a specific environment as compared to a similar degrading agent or detecting agent without the improvement (e.g., plurality of strong bonds).Associating

[0086] In accordance with various embodiments, any application-appropriate manner of associating a sample with a degrading agent or a detecting agent to form a degradation complex or a detection complex, respectively, may be used. In some embodiments, association may be or include adsorption (e.g., adhesion of atoms, ions, or molecules from a gas, liquid or dissolved solid to a surface), mechanical adhesion (e.g., type of adhesion where materials interlock, other examples may include sewing, velcro, and some textile adhesives), chemical adhesion (e.g., two materials from a compound by various types of bonds), dispersive adhesion (e.g., two materials attract due to intermolecular interactions between molecules of each material), diffusive adhesion (e.g., materials join by diffusion), absorption (e.g., atoms, molecules or ions enter some bulk phase - liquid or solid material). In some embodiments, associating may be performed under a variety of different conditions (e.g., thermal activation, pressure activation, illumination activation, pH) in various environments (e.g., liquid, gas stream) as appropriate for a particular embodiment. In some embodiments, use of such conditions may further boost the efficiency, reduce the cost of the process, or any combination thereof.

[0087] In certain embodiments, association between a sample and a degrading agent leads to a decrease in the level of PFAS in the sample. In certain embodiments, this process may have exponential nature. FIG. 5 demonstrates a set of example results for PFAS associating with the degrading agent, whereas 501 shows PFAS concentration decrease with time in the presence of the degrading agent and 502 shows removal percentage increase with time in the presence of the degrading agent.

[0088] In some embodiments, association between a sample and a degradation agent or a detecting agent may occur at a particular pH (e.g., a pH between 6.5-7.5). In someembodiments, association between a sample and a degradation agent or a detecting agent may occur at least one of an elevated temperature and an elevated pressure. In some embodiments, association between a sample and a degradation agent or a detecting agent may occur at room temperature and normal pressure (i.e., approximately 1 bar).Exposing

[0089] In accordance with various embodiments, when exposing a degradation complex to one or more degradation activators or a detection complex to one or more detection activators, any of a variety of exposing methods and conditions may be used. For example, in some embodiments, exposing may be or comprise applying a gas including or suspected of including one or more PFAS to a degradation complex. In some embodiments, a gas may be or comprise at least one of hydrogen and inert gas (e.g., nitrogen, argon). In some embodiments, exposing may be or comprise applying a liquid including one or more PFAS to a degradation complex or a detection complex.Degradation and Detection Activators

[0090] In some embodiments, degradation activators or detection activators may, for example, be or comprise: a gas (e.g., hydrogen gas, nitrogen gas), a liquid, illumination (e.g., visible illumination, ultraviolet illumination, near-infrared illumination, infrared illumination, microwave illumination), electronic discharge (e.g., plasma activation, electrical activation), external conditions (e.g., temperature, pressure, pH, ionic strength, surfactants), or any combination thereof. In certain embodiments, exposing one or more degradation activators to a degradation complex may be non-linear in time (e.g., pulsed, oscillating, dosing) or in space.

[0091] In certain embodiments, exposure may lead to modifying one or more PFAS (e.g., into a different compound by breaking carbon-halogen bonds, mineralization). In certain embodiments, this process may have exponential nature.Regeneration and Reuse

[0092] In certain embodiments, at least a portion of the degrading agent or at least a portion of the detection agent may be regenerated (e.g., renewed) after the association and / or exposure process. In certain embodiments, the regeneration comprises exposing at least a portion of the degrading agent or a detection agent to a solvent (e.g., methanol, ethanol), exposing at least a portion of the degrading agent or the detection agent to an acid, exposing at least a portion of the degrading agent or the detection agent to an elevated temperature, or any combination thereof. In certain embodiments, regenerating at least a portion of the degrading agent or the detection agent after the association and / or exposure process allows for reuse of the degrading agent or detection agent, respectively, on an additional sample.

[0093] In certain embodiments, the performance of the degrading agent in the association process may be defined as related to the PFAS decrease in a sample. In certain embodiments, the performance of the degrading agent in the association process may be defined as the rate of PFAS decrease in a sample. In certain embodiments, the performance of the degrading agent after the regeneration is at least 70%, 80%, or 90% as compared to the performance before the regeneration. In certain embodiments, the regeneration of at least a portion of the degrading agent may be performed at least 3, 5, or 10 times, for example, without a loss of performance of the degrading agent of more than 10%, 20%, or 30% as compared to the degrading agent’s performance before regeneration.

[0094] In certain embodiments, the performance of the detecting agent may be defined as related to the ability to detect certain PFAS concentration in a sample (e.g., sensitivity, response time, signal-to-noise ratio). In certain embodiments, the performance of the detecting agent after regeneration is at least 70%, 80%, or 90% as compared to the performance before the regeneration. In certain embodiments, the regeneration of at least a portion of the detecting agent may be performed at least 3, 5, or 10 times, for example, without a loss of performance of the detecting agent of more than 10%, 20%, or 30% as compared to the detecting agent’s performance before regeneration.

[0095] In some embodiments, performance of a degrading agent may be defined as the amount of PFAS transformation per unit of time or other applicable parameter (e.g., volume). In some embodiments, the performance of the degrading agent in the exposure process may be defined as the rate of PFAS transformation. In certain embodiments, the performance of thedegrading agent after the regeneration is at least 70%, 80%, or 90% as compared to before regeneration. In some embodiments, PFAS transformation may be defined as being or including C-F bond breakage.Methods of Making a Detecting Agent and / or a Degrading Agent

[0096] FIG. 6 is a schematic that represents an exemplary degrading and / or detecting agent 600. In certain embodiments, a degrading agent may comprise a substrate 601, a buffer layer, a plurality of nanoscale attachments 602. In certain embodiments, a degrading agent may further comprise a capture agent 603. Examples of substrates and nanoscale attachments may be as described elsewhere herein.Buffer Layer

[0097] In certain embodiments, a buffer layer may be or comprise a silica coating. A buffer layer may create binding sites to at least one of improve adhesion and increase density of nanoscale attachments. In certain embodiments, a deposition process used to create a buffer layer may be or include a plasma enhanced chemical vapor deposition reaction.

[0098] In some embodiments, a chemical vapor deposition reaction comprises exposing a substrate to a mixture of hexa-methyldisiloxane (HMDSO) and oxygen for a period of time between about 5 and about 20 minutes. The thickness of the buffer layer may be between about 1 nm and about 50 nm. In certain embodiments, the buffer reaction includes at least one of pretreatment and post-treatment steps (e.g. cleaning, surface activation, surface passivation).

[0099] FIG. 7 is a schematic that represents an example system 700 to form a buffer layer. The system 700 may comprise inlets for oxygen 701, argon 702, HMDSO 703 that lead to a reaction chamber 704. The reaction chamber may comprise a vacuum pump 707, a microwave source 706, and a substrate 705 for the reaction.Altering Wettability

[0100] In certain embodiments, a degrading agent or a detecting agent may have specific wettability properties. In certain embodiments, specific wettability properties may improve at least one of an association process of a sample with a degrading agent and an exposure process of a degradation activator and a degradation complex. In certain embodiments, specific wettability properties may improve at least one of an association process of a sample with adetection agent and an exposure process of a detection activator and a detection complex. In certain embodiments, a degrading agent or a detecting agent has a liquid (e.g., water) contact angle of less than 30°, 20°, 10°. In certain embodiments, a degrading agent or a detecting agent has a liquid (e.g., water) contact angle of more than 150°, 160°, 170°. In certain embodiments, alteration of a water contact angle may be varied (e.g., enhanced) via a method of making a degrading agent or a detecting agent that comprises: (a) dry plasma treatment for a short duration (e.g., 5 s); (b) coating with a sol-gel silica coating followed by controlled heating.EXAMPLES

[0101] The following examples further demonstrate various embodiments. One of ordinary skill in the art will appreciate that certain conditions and specific values as described herein may be changed as desired.Example 1: Making a Degrading or a Detecting Agent

[0102] Described herein is an embodiment of a method for making a degrading or a detecting agent that comprises a substrate, nanoscale attachments, and a capture agent (see FIG.6)

[0103] In this Example, a reticulated vitreous carbon foam (porosity 98%) was used as a substrate on which a buffer layer was formed. The buffer layer was formed by performing silica deposition in a microwave plasma reactor, where the substrate was first activated in oxygen environment at a power of 225 W, then exposed to a mixture of hexa-methldisiloxane (HMDSO) and oxygen in 300 W microwave power. The process resulted in a thin layer of -SiCh- molecular groups attached on all open surfaces.

[0104] Subsequently, nanoscale attachments in the form of carbon nanotubes (CNTs) were grown on a substrate in a programmable furnace using a floating catalyst chemical vapor deposition (CVD) method, where the entire thermal CVD process contained three stages: preheat, growth and controlled cooling. Pre-heat and controlled cooling were performed under inert environment, while in the growth stage, a mixture of xylene (carbon source) and ferrocene (catalyst) was injected into the reactor with a flowing gas mixture of argon and hydrogen at 375°C. The substrate was kept at 700 °C subject to the deposition for a period of time between 20 minutes and 5 hours. The substrate was allowed to cool overnight in argon. At the end of this process a layer of aligned carbon nanotubes was formed and associated with the substrate (also referred to herein as a “nanoparticle carpet”).

[0105] Finally, capture agents in the form of palladium nanoparticles were formed on the surface of carbon nanotubes by a liquid-phase synthetic approach. The steps involved: (a) soaking the nanoscale attachments in a tetra-amine palladium nitrate (TAPN) precursor solution of optimized concentration (1-20 mM varies with a substrate condition) and time; (b) recovering the nanoscale attachments from the tetra-amine palladium nitrate solution; (c) washing-off the excess of the solution from the nanoscale attachments by briefly rinsing in methanol and deionized (DI) water; (d) drying the nanoscale attachments at 100 °C; (e) calcinating the nanoscale attachments at 400 °C in inert atmosphere (e.g. argon), (f) annealing the nanoscale attachments at 450 °C in reducing environment containing hydrogen balanced argon. Pd nanoparticles were be formed with an average size between about 10 nm and about 15 nm.

[0106] The resulting degrading or detecting agents were characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) to benchmark structural information of the element (e.g., overall nanoscale attachment distribution in different parts of the substrate, spacing between individual nanoscale attachments, average height of the nanoscale attachments, degree of orientation of the nanoscale attachments, and entanglement of the nanoscale attachments, geometry and size distribution of the capture agents, see FIG. 3). The overall compositional analysis of the sensing element material were performed with Energy Dispersive Spectroscopy (EDS) attached to the SEM. Surface chemical bonding states of the outer atomic layers (depth resolution in 1-10 nm) were analyzed using X-ray Photoelectron Spectroscopy (XPS). Crystallographic information was obtained using X-Ray Diffraction (XRD). Specific surface area, porosity and micromeritics information was obtained by the gas adsorption Brunauer-Emmett-Teller (BET) technique, which enables multi-point measurement of specific surface area (m2 / g) through gas adsorption analysis. Graphitic quality (sp2-sp3bond ratio) of the nanotubes was analyzed using Raman Spectroscopy.Example 2: Degrading Agents Using Other Nanoparticles as Capture Agents

[0107] Below are examples of other nanoparticle-based compositions that may be used in making degrading agents or detecting agents in combination with or without palladium nanoparticles as described above. For purposes of the following examples, preparation of the substrate and nanoscale attachments are as described in Example 1 unless otherwise specified.Palladium Nanoparticles with an Oxide Shell

[0108] Palladium nanoparticles with oxide shell are formed by oxidizing palladium nanoparticles by heating the nanoparticles in ambient environment (e.g., 250 °C for 2 hours).Bimetallic Nanoparticles

[0109] Bimetallic silver-palladium nanoparticles are fabricated by depositing silver films on palladium nanoparticles using a liquid phase approach. Deposition of silver is performed by infiltrating the substrate supported nanoparticles with silver nitrate precursor solution and subsequently heating it at 40 °C using dimethyl sulfoxide (DMSO) as reducing agent and sodium citrate as capping agent. The samples are removed from the solution after 2 hours and rinsed with water followed by air drying for 24 hours. The silver synthesis process was carried out in a dark room to avoid degradation of silver nitrate under visible light.Titanium Oxide Nanoparticles

[0110] To form titanium oxide nanoparticles, titanium dioxide (TiCh) powder is mixed in water under slow stirring rate at room temperature for 15 min. The resulting solution is used to infiltrate a substrate, then dry it at 100 °C for 24 h followed by annealing at 500 °C for 1 h.Tungsten-Based Systems

[0111] To form tungsten oxide (WO3) nanoparticles, a hydrothermal reaction with peroxo-tungstic acid (PTA) solution is used. First, 0.025 M solution of Na2WO4-2H2O (0.825 g) is prepared in 93 mL of water under stirring for 10 min. The solution is acidified by adding 2 mb of HC1 and stirred for 1 h, 5 mL of H2O2 is added to the acidified solution to convert the solution to peroxo-tungstic acid. A substrate is wetted and immersed into the peroxo-tungstic acid solution and subjected to hydrothermal reaction for 4 hrs at 150 °C. The hydrated substrates are subsequently removed from solution and rinsed repeatedly until the pH is above 6. Last, the resulting substrate is annealed at 500 °C for 2 hrs with a heating rate of 5 °C / min.

[0112] To form tungsten oxide nanoparticles with dopants (e g., MXWI.X02, where M is Hf or other transition metal), a salt of the doping metal is added in measured proportion to the tungsten precursor. For example, HfCh is added into the solution of Na2WC>4 to form hafnium doped tungsten oxide for electrochemical detection of perfluorooctanoic acid (PFOA).

[0113] To form tungsten sulfide nanoparticles, a hydrothermal method is used. The precursor consists of Na2WC>4 2H2O and thiourea in which a substrate is soaked for 1 h. The resulting mixture is heated for 12 h at 180 °C in a Teflon-lined hydrothermal synthesis autoclave reactor.Example 3: Non-Nanoparticle Capture AgentsIonomers

[0114] In this Example, ionomer-based capture agents are used (e.g., for detection applications). Selected ionomers are added to a mixture of isopropanol (iPA) and N,N Dimetyl acetamide (DMAC). This mixture is associated with at least a portion of the nanoscale attachments, then dried for few minutes at room temperature, followed by vacuum drying for 3-5 mins.Enzyme-Based Systems

[0115] In this Example, enzyme-based capture agents are used. To form capture agents, a plurality of nanoscale attachments is immersed into a solution of one or more selected enzymes to immobilize the enzymes themselves, for example, in the presence of specific polymers, surfactants, and / or linking molecules that further aid in enzyme adsorption to at least a portion of the nanoscale attachments. This method may preserve properties of immobilized enzymes. Alternatively, enzymes are attached to at least a portion of the nanoscale attachments using a linking agent, such as glutaraldehyde, which is a common cross-linking agent for enzyme immobilization, this method may provide strong anchoring effect, creating durable, robust and controllable immobilized enzymes. The procedure involves immersing the at least a portion of the nanoscale attachments into a solution with a linking agent, then washing out the excess with water, then immersing a degrading or detecting agent into a solution with an enzyme.Example 4: Adsorbing and Detecting PFAS

[0116] Described herein is an embodiment of a method adsorbing and detecting PFAS.

[0117] PFAS adsorption in water samples were carried out in batch reactors consisting of 1 liter polypropylene (PP) bottle containing a degrading agent prepared as in Example 1 (FIG. 8). The batch reactor setup 800 included a bottle 801 with an inlet 802, outlet 803, and an additional port 804. The inlet contained a valve 805. The outlet contained a pressure meter 805. The IL PFAS solution was prepared by mixing the selected PFAS stock solution with Milli-Q water. The additional port was used for a syringe 807. For example, an aqueous sample solution containing known concentration of perfluorooctanoic acid (PFOA) was injected into the reactor using the syringe to the target concentration. The pH was monitored using a pH meter. The reactor was then placed on a magnetic stirrer 808 mixed with stir bar, with a stirring speed of 200 rpm. Additionally, the reactor was connected to a hydrogen gas line (20% hydrogen balance nitrogen) for Pd based catalysis / degradation tests. Degrading agents 809 were attached to a tantalum (TA) wire 810, hanged inside the bottle, and immersed in Milli-Q water, with a total mass ~ 200mg.

[0118] Aliquot specimen of 2 m was derived from the bottles using a syringe at specified time intervals. Specimens collected in the syringe at different reaction times were filtered using disposable polytetrafluoroethylene syringe filters. Initially, a 2 mL aliquot specimen was discarded by running it through the filter in order to saturate the filter and then the remaining liquid specimen was collected through the saturated filter in a 2 mL vial for high- performance liquid chromatography analysis (EPA approved LC-MS / MS protocol for PFAS). FIG. 5 shows PFOA removal from a water sample at pH 7 over several hours by adsorbing to a degrading agent with PFOA concentration in the sample decreasing over time, reaching greater than 90% removal.

[0119] For detection, three electrodes electrochemical system was employed as shown in FIG. 9. The detection agent acted as the working electrode, a silver chloride electrode (Ag / AgCl) as a reference electrode and a platinum wire as a counter electrode. Its electrochemical response was measured in cyclic voltammetry (CV) and square wave voltammetry (SWV), electrochemical impedance spectroscopy (EIS), and the representative features were extracted from the obtained signals. FIG. 10 shows electrochemical signalsobtained from three detection agents operating in 0.02 M PBS buffer at pH 7. The detection agents include “CNT” - without any nanoparticles 1001-1002, “CNT-WO3” - with tungsten oxide nanoparticles 1003-1004, and “CNT-Pd” - with palladium nanoparticles 1005-1006. Both SWV 1002, 1004, and 1006 (performed at 15 Hz) and CV 1001, 1003, and 1005 (performed at 20mV / sec) plots differentiate PFOA concentrations of 0.1, 1, and 5 ppm. Signals for SWV were control (e.g., pure buffer) corrected.Example 5: PFAS Degradation

[0120] For PFAS degradation, degrading agents that have adsorbed PFAS as described in Example 3 (pre-detection step) are placed in the reactor, with the same set-up of experiment conditions. The PFAS solution is bubbled by high purity hydrogen-nitrogen gas mixture acting as a degradation activator.Example 6: Another Example of PFAS Adsorption

[0121] Described herein is an embodiment of a method adsorbing PFAS. For testing the PFAS adsorption capability of CNT materials, an end-to-end rotator was used. A sample was continuously rotated in a test PFOA solution. Aliquot specimen were derived at specific time intervals as discussed in Example 4 for monitoring how a composition of the sample changes.

[0122] FIG. 11A shows that PFOA concentration in water decreases in the presence of CNT sample from a starting concentration around 250 ppb to around 0 within few hours. The results demonstrate that the CNT sample efficiently adsorbs PFOA. To check recovery / regeneration of the sample, a desorption experiment was carried out using ethanol as a rinsing agent.

[0123] FIG. 11D shows results of desorption tests for various air-dried samples under different conditions. Specifically, a value of CzC represents a ratio between PFOA concentration stored in a sample (Co) and PFOA concentration released by the sample (C) as measured in ethanol and adjusted to a volume difference between ethanol and the sample. A value of 1 for C / Co represents complete PFOA from a sample into ethanol. FIG. 11D shows that a CNT sampledemonstrated 100% desorption, demonstrating an efficient regeneration process by alcohol rinsing.Example 7: Another Example of PFAS Degradation

[0124] PFAS degradation was carried out in a batch reactor as shown in FIG. 8. After adsorption, samples were retrieved from PFAS solution, dried in air for 3 days, exposed to a degradation procedure, and finally immersed in ethyl alcohol to run the desorption test. This immersion process results in release of any adsorbed PFAS that has not been degraded on the surface of a sample into alcohol. If no degradation occurred, PFAS entire amount would be released.A. Degradation through plasma treatment of adsorbate

[0125] One degradation procedure comprised plasma treatment. FIG. 11D shows desorption tests for CNT samples that underwent 5 and 10 sec oxygen plasma treatment with a power of 115 W and oxygen rate of 48 mL / min. Relative PFOA concentration detected after treatment was approximately 70% and 65%. This result demonstrates that plasma treatment degrades PFOA and that prolonged exposure increases PFOA degradation.B. Degradation by hydrogen gas

[0126] CNT samples attached with Pd nanoparticles (PdCNT), with structural architecture as shown in FIG. 6, were used for PFAS degradation using flowing hydrogen (20% hydrogen balanced by argon with a flow rate of 1 sL / min). FIG. 11B shows that PFOA concentration in water decreased from 250 ppb to approximately 180 ppb in the presence of PdCNT samples with flowing hydrogen. The adsorption capacity of PdCNT samples was less than that of CNT samples shown in FIG. 11 A. The samples subsequently did not release any PFOA during rinsing with ethanol, indicating that all the PFOA was degraded during the adsorption. The decreased adsorption by PdCNT samples may be due to hydrogen gas mixture bubbles hindering the adsorption process.

[0127] PdCNT samples were further tested without hydrogen bubbling during adsorption. FIG. 11C shows that PFOA concentration in water decreased from 250 ppb to approximately 0 ppb within 1 hour in the presence of PdCNT samples without any hydrogen. After sample dryingfor 3 days, a desorption was performed in the presence of flowing hydrogen to degrade PFOA. FIG. 11D shows that PdCNT samples in the presence of hydrogen desorb approximately 70% of available PFOA after 30 min exposure. The results indicate that approximately 30% of PFOA is degraded. Longer exposure times may further result in more significant degradation. However, hydrogen bubbling may evaporate ethanol. Other measurements are performed in gas tight reactors to prevent hydrogen bubbling from evaporating alcohol.EMBODIMENTSThe following numbered embodiments are contemplated.1. A method for degrading Per- and Poly-fluoroalkyl Substances (PFAS) comprising providing a sample comprising one or more PFAS; associating the sample with a degrading agent to form a degradation complex; and exposing at least a portion of the degradation complex to one or more degradation activators.2. The method of embodiment 1, wherein the sample is or comprises a gas or a liquid.3. The method of embodiment 2, wherein the sample is or comprises air, water, industrial waste, foodstuffs, cleaning products, shampoo.4. The method of embodiment 1 or embodiment 2, further comprising a step of pretreating the sample (e.g., mechanical filtration, pH adjustment, removal of chlorine, iron, surfactants, total organic carbon).5. The method of any one of the above embodiments, wherein the associating comprises at least one member selected from the group consisting of causing surface contact, adsorption, mechanical adhesion, chemical adhesion, dispersive adhesion, diffusive adhesion, infiltration through pores.6. The method of any one of the above embodiments, wherein the exposing occurs at room temperature and / or normal pressure (i.e. approximately 1 bar).7. The method of any one of the above embodiments, wherein the exposing occurs in a gas stream or in a liquid.8. The method of any one of the above embodiments, wherein the one or more degradation activators comprise hydrogen or a mixture of hydrogen and nitrogen gases.9. The method of any one of the above embodiments, wherein the one or more degradation activators comprise at least one member selected from the group consisting of hydrogen gas, nitrogen gas, visible illumination, ultraviolet illumination, near-infrared illumination, infrared illumination, microwave illumination, plasma activation, electrical activation.10. The method of any one of the above embodiments, further comprising regenerating (e.g., renewing) at least a portion of the degrading agent after associating the sample with the degrading agent and / or exposing to the one or more degradation activators.11. The methods of embodiments 10, wherein the regenerating is or comprises exposing at least a portion of the degrading agent to a solvent (e g., methanol and / or ethanol), exposing at least a portion of the degrading agent to an acid, or exposing at least a portion of the degrading agent to an elevated temperature.12. The method of any one of the above embodiments, wherein PFAS are present in the sample with one or more co-contaminants.13. The method of embodiment 12, wherein the one or more co-contaminants is or comprises a metal, a salt, or organic matter.14. The method of any one of the above embodiments, further comprising modifying one or more PFAS (e.g., into a different compound by breaking carbon-fluorine bonds) after theexposing of at least a portion of the degradation complex to the one or more degradation activators.15. The method of any one of the above embodiments, wherein at least a portion of the method is performed in and / or connected to a water treatment system (e.g., purification system, filtration system, distillation system, reverse osmosis system, ion exchange system, disinfection system, electrochemical system).16. A system for degrading Per- and Poly-fluoroalkyl Substances (PFAS) by performing the method of any one of the above embodiments.17. A method of making a degrading agent or a detecting agent comprising providing a substrate, applying a deposition reaction to at least a portion of the substrate to form a buffer layer, and applying a chemical vapor deposition reaction to at least a portion of the buffer layer to form a plurality of nanoscale attachments on the substrate.18. The method of embodiment 17, further comprising associating a plurality of nanoparticles or a nanolayer with at least a portion of the plurality of nanoscale attachments.19. The method of embodiment 18, wherein the nanoparticles are or comprise a metal or an oxide.20. The method of embodiment 19, wherein the metal is or comprises palladium.21. The method of embodiment 18 or embodiment 19, wherein the oxide is or comprises a photocatalyst.22. The method of embodiment 18, wherein the nanoparticles are or comprise a sulfide, a carbide, or a polymeric moiety.23. The method of embodiment 17 or embodiment 18, comprising attaching one or more catalytic agents to at least a portion of the plurality of nanoscale attachments and / or the nanoparticles.24. The method of any one of embodiments 17-23, wherein the substrate maintains its structural integrity to at least 700 °C.25. The method of any one of embodiments 17-24, wherein the substrate is or comprises at least one of a carbon structure (e.g., foam, cloth, pellets, paper, fabric), ceramic material, glass, an oxide or metal foam.26. The method of any one of embodiments 17-25, wherein the deposition reaction is a plasma enhanced chemical vapor deposition reaction.27. The method of embodiment 26, wherein the chemical vapor deposition reaction comprises exposing at least a portion of the substrate to a mixture of precursor materials (e.g., hexa-methyldisiloxane or HMDSO) and gases (e.g., oxygen).28. The method of any one of embodiments 17-27, wherein the thickness of the buffer layer is between about 1 nm to about 50 nm.29. The method of any one of embodiments 17-28, wherein the plurality of nanoscale attachments is or comprises a layer of one-dimensional nano-structures.30. The method of embodiment 29, wherein the layer of one-dimensional structures are or comprises nanotubes (e.g., carbon, nitride, carbide, oxide, metal).31. The method of embodiment 29 or embodiment 30, wherein at least a portion of the layer of one-dimensional structures is covalently bonded to the substrate.32. The method of embodiment 29, wherein the layer of nanotubes is between about 1 pm to about 2000 jam in height.33. The method of embodiment 29 or embodiment 32, wherein the layer of nanotubes has an average density between about 10 to about 1,000 units per pm2.34. The method of any one of the embodiments 29-33, wherein the layer of nanotubes has an average diameter between about 5 to about 30 nm.35. The method of any one of the embodiments 29-34, wherein the layer of nanotube has an estimated specific surface area between about 70 to about 150 m2 / g.36. The method of any one of embodiments 17-35, comprising at least one of: plasma oxygen coating on the nanotubes for a short duration (e.g., 5 s), coating the layer of nanotubes with a solgel silica coating followed by controlled heating.37. A degrading agent or a detecting agent comprising a substrate, and a plurality of nanoscale attachments associated with the substrate, wherein the plurality of nanoscale attachments is formed by liquid or vapor phase treatments.38. The degrading agent or the detecting agent of embodiment 37, further comprising a plurality of capture agents associated with at least a portion of the plurality of nanoscale attachments.39. The degrading agent or the detecting agent of embodiment 37 or embodiment 38, wherein a plurality of capture agents are or comprise nanoparticles.40. The degrading agent or the detecting agent of any one of embodiments 37-39, wherein the substrate maintains its structural integrity to at least 700 °C.41 . The degrading agent or the detecting agent of any one of embodiments 37-40, wherein the substrate is or comprises at least one of a carbon structure (e.g., foam, cloth, pellets, paper, fabric), ceramic material, glass, an oxide, a metal foam.42. The degrading agent or the detecting agent of any one of embodiments 37-41, wherein the plurality of nanoscale attachments is or comprises a layer of nanotubes (e.g., carbon, boron nitride).43. The degrading agent or the detecting agent of embodiment 42, wherein the layer of nanotubes is between about 1 pm to about 2000 pm in height.44. The degrading agent or the detecting agent of embodiment 42 or 43, wherein the layer of nanotubes has an average density between about 10 to about 1000 units per pm2.45. The degrading agent or the detecting agent of any one of embodiments 42-44, wherein the layer of nanotubes has an average diameter between about 2 to about 30 nm.46. The degrading agent or the detecting agent of any one of embodiments 42-45, wherein the layer of nanotube has an estimated specific surface area between about 70 to about 150 m2 / g.47. The degrading agent or the detecting agent of any one of embodiments 39-46, wherein at least a portion of the nanoparticles are or comprise metallic Pd nanoparticles with an average diameter between about 2 nm to about 50 nm.48. The degrading agent or the detecting agent of any one of embodiments 39-47, wherein at least a portion of the nanoparticles are or comprises at least one type of nanoparticle with catalytic properties [e.g., metallic catalysts such as palladium, semiconductor nanoparticles (e.g., ZnS, CdTe, HgSe, heterojunction semiconductors); oxides (e.g., TiO2, ZnO, WO3); plasmonic materials (e.g., gold, silver), alloys; composites; metal-organic frameworks; covalent organic frameworks; hydrogen-bonded organic frameworks].49. The degrading agent or the detecting agent of any one of embodiments 39-48, wherein at least a portion of the nanoparticles are or comprise WO3 nanoparticles.50. The degrading agent or the detecting agent of any one of embodiments 39-49, wherein at least a portion of the nanoparticles are or comprise TiCh nanoparticles.51. A method for detecting Per- and Poly-fhioroalkyl Substances (PFAS) comprising providing a sample; associating the sample with a detecting agent to form a detection complex if the sample comprises one or more PFAS; receiving a signal from the detection complex, wherein the signal indicates a presence of one or more PFAS in the sample.52. The method of embodiment 51, wherein the signal comprises at least one member selected from the group consisting of an electrical, electrochemical, optical, thermal, and / or chemical signal.53. The method of embodiment 51 or 52, wherein the strength of the signal is related to a PFAS concentration of one or more PFAS.54. The method of any one of embodiment 51-53, wherein the sample is or comprises a gas or a liquid.55. The method of any one of embodiments 51-54, wherein the sample is or comprises air, water, industrial waste, foodstuffs, cleaning products, shampoo.56. The method of any one of embodiments 51-55, further comprising a step of pretreating the sample (e.g., to remove chlorine, iron, surfactants, total organic carbon).57. The method of any one of embodiments 51-56, wherein the associating comprises at least one member selected from the group consisting of causing surface contact, adsorption, mechanical adhesion, chemical adhesion, dispersive adhesion, diffusive adhesion, infiltration through pores.58. The method of any one of embodiments 51-57, wherein PFAS are present in the sample with one or more co-contaminants.59. The method of embodiment 58, wherein the one or more co-contaminants is or comprises a metal, a salt, or organic matter.60. The method of any one of embodiments 51-59, wherein at least a portion of the method is performed in and / or connected to a water treatment system (e.g., purification system, filtration system, distillation system, reverse osmosis system, ion exchange system, disinfection system, electrochemical system).61. The method of any one of embodiments 51-60 further comprising, exposing at least a portion of the detection complex to one or more detection activators.62. The method of any one of embodiments 51-61, wherein the exposing occurs at room temperature and / or normal pressure (i.e. approximately 1 bar).63. The method of any one of embodiments 51-62, wherein the exposing occurs in a gas stream or in a liquid.64. The method of any one of embodiments 51-63, wherein the one or more detection activators comprise at least one member selected from the group consisting of hydrogen gas, nitrogen gas, visible illumination, ultraviolet illumination, near-infrared illumination, infrared illumination, microwave illumination, plasma activation, electrical activation.65. The method of any one of embodiments 51-64, further comprising regenerating (e g., renewing) at least a portion of the detecting agent after associating the sample with the detecting agent and / or exposing to the one or more detection activators.66. The methods of embodiment 65, wherein the regenerating is or comprises exposing at least a portion of the detecting agent to a solvent (e.g., methanol and / or ethanol), exposing at least a portion of the detecting agent to an acid, or exposing at least a portion of the detecting agent to an elevated temperature.67. The method of any one of embodiments 51-66, further comprising modifying one or more PFAS (e.g., into a different compound by braking carbon-fluorine bonds) after the exposing of at least a portion of the detection complex to the one or more detection activators.68. A system for detecting Per- and Poly-fluoroalkyl Substances (PFAS) by performing the method of any one of embodiments 51-67.

Claims

CLAIMSWhat is claimed is:

1. A method for degrading Per- and Poly-fluoroalkyl Substances (PFAS) comprising providing a sample comprising one or more PFAS; associating the sample with a degrading agent to form a degradation complex; and exposing at least a portion of the degradation complex to one or more degradation activators.

2. The method of claim 1, wherein the sample is or comprises a gas or a liquid.

3. The method of claim 2, wherein the sample is or comprises air, water, industrial waste, foodstuffs, cleaning products, shampoo.

4. The method of claim 1 or claim 2, further comprising a step of pretreating the sample.

5. The method of claim 1, wherein the associating comprises at least one member selected from the group consisting of causing surface contact, adsorption, mechanical adhesion, chemical adhesion, dispersive adhesion, diffusive adhesion, infiltration through pores.

6. The method of claim 1, wherein the exposing occurs at room temperature and / or normal pressure.

7. The method of claim 1, wherein the exposing occurs in a gas stream or in a liquid.

8. The method of claim 1,wherein the one or more degradation activators comprise hydrogen or a mixture of hydrogen and nitrogen gases.

9. The method of claim 1, wherein the one or more degradation activators comprise at least one member selected from the group consisting of hydrogen gas, nitrogen gas, visible illumination, ultraviolet illumination, near-infrared illumination, infrared illumination, microwave illumination, plasma activation, electrical activation.

10. The method of claim 1, further comprising regenerating at least a portion of the degrading agent after associating the sample with the degrading agent and / or exposing to the one or more degradation activators.

11. The methods of claim 10, wherein the regenerating is or comprises exposing at least a portion of the degrading agent to a solvent, exposing at least a portion of the degrading agent to an acid, or exposing at least a portion of the degrading agent to an elevated temperature.

12. The method of claim 1, wherein PF AS are present in the sample with one or more co-contaminants.

13. The method of claim 12, wherein the one or more co-contaminants is or comprises a metal, a salt, or organic matter.

14. The method of claim 1, further comprising modifying one or more PFAS after the exposing of at least a portion of the degradation complex to the one or more degradation activators.

15. The method of claim 1, wherein at least a portion of the method is performed in and / or connected to a water treatment system.

16. A system for degrading Per- and Poly-fluoroalkyl Substances (PFAS) by performing the method of any one of the above claims.

17. A method of making a degrading agent or a detecting agent comprising providing a substrate, applying a deposition reaction to at least a portion of the substrate to form a buffer layer, and applying a chemical vapor deposition reaction to at least a portion of the buffer layer to form a plurality of nanoscale attachments on the substrate.

18. The method of claim 17, further comprising associating a plurality of nanoparticles or a nanolayer with at least a portion of the plurality of nanoscale attachments.

19. The method of claim 18, wherein the nanoparticles are or comprise a metal or an oxide.

20. The method of claim 19, wherein the metal is or comprises palladium.

21. The method of claim 18 or claim 19, wherein the oxide is or comprises a photocatalyst.

22. The method of claim 18, wherein the nanoparticles are or comprise a sulfide, a carbide, or a polymeric moiety.

23. The method of claim 17 or claim 18, comprising attaching one or more catalytic agents to at least a portion of the plurality of nanoscale attachments and / or the nanoparticles.

24. The method of claim 17, wherein the substrate maintains its structural integrity to at least 700 °C.

25. The method of claim 17, wherein the substrate is or comprises at least one of a carbon structure, ceramic material, glass, an oxide or metal foam.

26. The method of claim 17, wherein the deposition reaction is a plasma enhanced chemical vapor deposition reaction.

27. The method of claim 26, wherein the chemical vapor deposition reaction comprises exposing at least a portion of the substrate to a mixture of precursor materials and gases.

28. The method of claim 17, wherein the thickness of the buffer layer is between about 1 nm to about 50 nm.

29. The method of claim 17, wherein the plurality of nanoscale attachments is or comprises a layer of onedimensional nano-structures.

30. The method of claim 29, wherein the layer of one-dimensional structures is or comprises nanotubes.

31. The method of claim 29 or claim 30, wherein at least a portion of the layer of onedimensional structures is covalently bonded to the substrate.

32. The method of claim 30, wherein the layer of nanotubes is between about 1 pm to about 2000 pm in height.

33. The method of claim 30,wherein the layer of nanotubes has an average density between about 10 to about 1,000 units per pm2.

34. The method of claim 30, wherein the layer of nanotubes has an average diameter between about 5 to about30 nm.

35. The method of claim 30, wherein the layer of nanotube has an estimated specific surface area between about 70 to about 150 m2 / g.

36. The method of claim 17, comprising at least one of: plasma oxygen coating on the nanotubes for a short duration, coating the layer of nanotubes with a sol-gel silica coating followed by controlled heating.

37. A degrading agent or a detecting agent comprising a substrate, and a plurality of nanoscale attachments associated with the substrate, wherein the plurality of nanoscale attachments is formed by liquid or vapor phase treatments.

38. The degrading agent or the detecting agent of claim 37, further comprising a plurality of capture agents associated with at least a portion of the plurality of nanoscale attachments.

39. The degrading agent or the detecting agent of claim 37 or claim 38, wherein a plurality of capture agents are or comprise nanoparticles.

40. The degrading agent or the detecting agent of claim 37, wherein the substrate maintains its structural integrity to at least 700 °C.41 . The degrading agent or the detecting agent of claim 37, wherein the substrate is or comprises at least one of a carbon structure, ceramic material, glass, an oxide, a metal foam.

42. The degrading agent or the detecting agent of claim 37, wherein the plurality of nanoscale attachments is or comprises a layer of nanotubes.

43. The degrading agent or the detecting agent of claim 42, wherein the layer of nanotubes is between about 1 pm to about 2000 pm in height.

44. The degrading agent or the detecting agent of claim 42 or 43, wherein the layer of nanotubes has an average density between about 10 to about 1000 units per pm2.

45. The degrading agent or the detecting agent of claim 42, wherein the layer of nanotubes has an average diameter between about 2 to about 30 nm.

46. The degrading agent or the detecting agent of claim 42, wherein the layer of nanotube has an estimated specific surface area between about 70 to about 150 m2 / g.

47. The degrading agent or the detecting agent of claim 39, wherein at least a portion of the nanoparticles are or comprise metallic Pd nanoparticles with an average diameter between about 2 nm to about 50 nm.

48. The degrading agent or the detecting agent of claim 39, wherein at least a portion of the nanoparticles are or comprises at least one type of nanoparticle with catalytic properties.

49. The degrading agent or the detecting agent of claim 39, wherein at least a portion of the nanoparticles are or comprise WO3 nanoparticles.

50. The degrading agent or the detecting agent of claim 39, wherein at least a portion of the nanoparticles are or comprise TiCh nanoparticles.

51. A method for detecting Per- and Poly-fluoroalkyl Substances (PFAS) comprising providing a sample; associating the sample with a detecting agent to form a detection complex if the sample comprises one or more PFAS; receiving a signal from the detection complex, wherein the signal indicates a presence of one or more PFAS in the sample.

52. The method of claim 51, wherein the signal comprises at least one member selected from the group consisting of an electrical, electrochemical, optical, thermal, and / or chemical signal.

53. The method of claim 51 or 52, wherein the strength of the signal is related to a PFAS concentration of one or more PFAS.

54. The method of claim 51, wherein the sample is or comprises a gas or a liquid.

55. The method of claim 51, wherein the sample is or comprises air, water, industrial waste, foodstuffs, cleaning products, shampoo.

56. The method of claim 51, further comprising a step of pretreating the sample.

57. The method of claim 51,wherein the associating comprises at least one member selected from the group consisting of causing surface contact, adsorption, mechanical adhesion, chemical adhesion, dispersive adhesion, diffusive adhesion, infiltration through pores.

58. The method of claim 51, wherein PFAS are present in the sample with one or more co-contaminants.

59. The method of claim 58, wherein the one or more co-contaminants is or comprises a metal, a salt, or organic matter.

60. The method of claim 51, wherein at least a portion of the method is performed in and / or connected to a water treatment system.

61. The method of claim 51 further comprising, exposing at least a portion of the detection complex to one or more detection activators.

62. The method of claim 61, wherein the exposing occurs at room temperature and / or normal pressure.

63. The method of claim 61, wherein the exposing occurs in a gas stream or in a liquid.

64. The method claim 61, wherein the one or more detection activators comprise at least one member selected from the group consisting of hydrogen gas, nitrogen gas, visible illumination, ultraviolet illumination, near-infrared illumination, infrared illumination, microwave illumination, plasma activation, electrical activation.

65. The method of claim 61, further comprisingregenerating at least a portion of the detecting agent after associating the sample with the detecting agent and / or exposing to the one or more detection activators.

66. The methods of claim 65, wherein the regenerating is or comprises exposing at least a portion of the detecting agent to a solvent, exposing at least a portion of the detecting agent to an acid, or exposing at least a portion of the detecting agent to an elevated temperature.

67. The method of claim 61, further comprising modifying one or more PFAS after the exposing of at least a portion of the detection complex to the one or more detection activators.

68. A system for detecting Per- and Poly-fluoroalkyl Substances (PFAS) by performing the method of any one of claims 51-67.

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